Aerobic C-C and C-O bond formation reactions mediated by high-valent nickel species

Nickel complexes have been widely employed as catalysts in C-C and C-heteroatom bond formation reactions. While Ni(0), Ni(I), and Ni(II) intermediates are most relevant in these transformations, recently Ni(III) and Ni(IV) species have also been proposed to play a role in catalysis. Reported herein is the synthesis, detailed characterization, and reactivity of a series of Ni(II) and Ni(III) metallacycle complexes stabilized by tetradentate pyridinophane ligands with various N-substituents. Interestingly, while the oxidation of the Ni(II) complexes with various other oxidants led to exclusive C-C bond formation in very good yields, the use of O₂ or H₂O₂ as oxidants led to formation of appreciable amounts of C-O bond formation products, especially for the Ni(II) complex supported by an asymmetric pyridinophane ligand containing one tosyl N-substituent. Moreover, cryo-ESI-MS studies support the formation of several high-valent Ni species as key intermediates in this uncommon Ni-mediated oxygenase-type chemistry.

The paper was published recently in Royal Society of Chemistry’s flagship journal Chemical Science:

S.M. Smith, O. Planas, L. Gñmez, N.P. Rath, X. Ribas, and L.M. Mirica
“Aerobic C-C and C-O bond formation reactions mediated by high-valent nickel species”
Chem. Sci. 2019, ASAP [abstract]
DOI: 10.1039/C9SC03758F